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@ARTICLE{Jovanovic:907825,
author = {Jovanovic, Sven and Riegger, Luise M. and Otto, Svenja-K.
and Sadowski, Marcel and Kötz, Olaf and Harm, Sascha and
Balzat, Lucas G. and Merz, Steffen and Burkhardt, Simon and
Richter, Felix H. and Sann, Joachim and Eichel, Rüdiger-A.
and Lotsch, Bettina V. and Granwehr, Josef and Albe, Karsten
and Janek, Jürgen},
title = {{I}nstability of the {L}i7{S}i{PS}8 {S}olid {E}lectrolyte
at the {L}ithium {M}etal {A}node and {I}nterphase
{F}ormation},
journal = {Chemistry of materials},
volume = {34},
number = {8},
issn = {0897-4756},
address = {Washington, DC},
publisher = {American Chemical Society},
reportid = {FZJ-2022-02236},
pages = {3659 - 3669},
year = {2022},
abstract = {Thiophosphate solid electrolytes containing metalloid ions
such as silicon or germanium show a very high lithium-ion
conductivity and the potential to enable solid-state
batteries (SSBs). While the lithium metal anode (LMA) is
necessary to achieve specific energies competitive with
liquid lithium-ion batteries (LIBs), it is also well known
that most of the metalloid ions used in promising
thiophosphate solid electrolytes are reduced in contact with
an LMA. This reduction reaction and its products formed at
the solid electrolyte|LMA interface can compromise the
performance of an SSB due to impedance growth. To study the
reduction of these metalloid ions and their impact more
closely, we used the recently synthesized Li7SiPS8 as a
member of the tetragonal Li10GeP2S12 (LGPS) family.
Stripping/plating experiments and the temporal evolution of
the impedance of symmetric Li|Li7SiPS8|Li transference cells
show a severe increase in cell resistance. We characterize
the reduction of Li7SiPS8 after lithium deposition with in
situ X-ray photoelectron spectroscopy, time-of-flight
secondary-ion mass spectrometry, and solid-state nuclear
magnetic resonance spectroscopy. The results indicate a
continuous reaction without the formation of elemental
silicon. For elucidating the reaction pathways, density
functional theory calculations are conducted followed by ab
initio molecular dynamics simulations to study the interface
evolution at finite temperature. The resulting electronic
density of states confirms that no elemental silicon is
formed during the decomposition. Our study reveals that
Li7SiPS8 cannot be used in direct contact with the LMA, even
though it is a promising candidate as both a separator and a
catholyte material in SSBs.},
cin = {IEK-9},
ddc = {540},
cid = {I:(DE-Juel1)IEK-9-20110218},
pnm = {1223 - Batteries in Application (POF4-122) /
FestBatt-Charakterisierung - Methodenplattform
'Charakterisierung' im Rahmen des Kompetenzclusters für
Festkörperbatterien (13XP0176B)},
pid = {G:(DE-HGF)POF4-1223 / G:(BMBF)13XP0176B},
typ = {PUB:(DE-HGF)16},
UT = {WOS:000795962300007},
doi = {10.1021/acs.chemmater.1c04302},
url = {https://juser.fz-juelich.de/record/907825},
}